Synthetic resin compounds of the phthalocyanine series

ABSTRACT

New synthetic resin condensation products are prepared by condensing a chlormethylated copper phthalocyanine and a polyamide. The new polymers are used to improve the flocculation resistance of phthalocyanine pigments.

United States Patent McKay 1541 SYNTHETIC RESIN COMPOUNDS OF THEPHTHALOCYANINE SERIES [72] Inventor: Robert Bruce McKay, Kilmarnock,

Ayrshire, Scotland [73] Assignee: Cil a Geigy AG, Basel, Switzerland[22] Filed: Aug. 12, 1970 [21] Appl. No.2 63,345

[30] Foreign Application Priority Data Aug. 13,1969 Great Britain..40455/69 52 us. (:1. ..260/l8 N, 106/288 Q, 260/37 N 511 Int. Cl."cos; 51/14, C08h 11/14 [58] Field of Search ..260/37 N, 18 N, 314.5;

[56] References Cited UNITED STATES PATENTS l/1967 Chiddix 250/3145 1 1Sept. 12, 1972 3,1 16,275 12/1963 Gamlen ..260/3l4.5 3,148,933 9/1964Randall ..260/3 14.5 3 ,252,992 5/1966 Drenchko ..260/314.5 3,336,3328/1967 Stein ..260/314.5 2,859,219 11/1958 Randall ..260/3l4.5 3,336,1478/1967 Mitchell ..260/3 14.5

Primary Examiner--Morris Liebman Assistant Examiner-P. R. MichlAttorney-Wenderoth, Lind & Ponack [57] ABSTRACT New synthetic resincondensation products are prepared by condensing a chlormethylatedcopper phthalocyanine and a polyamide. The new polymers are used toimprove the flocculation resistance of phthalocyanine pigments.

13 Claims, No Drawings SYNTHETIC RESIN COMPOUNDS OF THE PHTHALOCYANINESERIES DETAILED DESCRIPTION ments in all their various forms suffer froma particular defect which is not shared by most other organic pigments.The defect in question manifests itself particularly in paints based ontitanium dioxide or other white inorganic pigment and the.phthalocyanine pigment,

especially in non-aqueousfsystems. If such paints are applied underdifferent'jconditions of shear,'widely different'strengthsof shade areobtained. Similarly, when paints or printing inks-containingphthalocyanine pigments are stored, the pigment'particles tend toaggregate with resulting loss of tinctorial strength and homogeneity ofthe paint or ink.

Many attempts have been made to try and overcome this flocculationproblem with varying degrees of success. Thus, for example, British Pat.specification No. 949,739 states that phthalocyanine pigment mixturesmay be rendered resistant to flocculation by incorporating therein from0.5 to mole percent of a phthalocyanine methylene amine having thegeneral wherein P represents a phthalocyanine radical, R is hydrogen oran unsubstituted or substituted aliphatic hydrocarbon radical, R is anunsubstituted or substituted aliphatic hydrocarbon radical, or, whentaken together with R a heterocyclic ring, and n is a number from 1 to4, preferably 3 or 4.

We have now found that by incorporating novel synthetic resincondensation products of chloromethylated phthalocyanine with reactivepolyamides into the phthalocyanine pigment tending to flocculate,pigment compositions are produced having surprisingly excellentflocculation-resistance combined with other desirable pigmentaryproperties such as high tinctorial power.

Accordingly, the present invention provides polymeric phthalocyaninepigment derivatives made from condensation of a chloromethylated copperphthalocyanine and a polyamide having a least one reactive amino group.

The term reactive amino group as used herein means any amino group inthe polymeric polyamide molecule which may enter into reaction with thechloromethylated phthalocyanine compound.

The chloromethylated phthalocyanine compounds used according to theinvention may be obtained for example according to the proceduredescribed in British Pat. specification No. 586,340. Advantageously,they contain a minimum of 5 percent by weight, based on the weight ofthe phthalocyanine, of chlorine atoms linked to the phthalocyaninenucleus through -CH groups. More preferably, the proportion of suchchlorine atoms is within the range of from 10 to 30 percent by weightbased on the weight of the phthalocyanine residue.

The reactive polyamides used according to the invention may becondensation products of polymeric fatty acids with polyamines,preferably in such ratio that the resulting polyamide resins possess anamine value in the range of from about 250 to 650 milligrams potassiumhydroxide per gram of resin. Polymeric fatty acids are advantageouslyrepresented by the reaction products obtained by polymerization of oneor more unsaturated long chain aliphatic or aromatic-aliphatic acids ortheir esters or otherderivatives easily converted into the acid.Suitable examples of such polymeric fatty acids are described in BritishPat. Nos. 878,985 and 841,554. Polymeric fatty acids or esters used forthe production'of reactive polyamides may also be epoxidized, forexample by reaction with peracetic acid performic acid or with hydrogenperoxide and formic acid or acetic acid. Suitable epoxidized fatty acidsand esters are described in British Pat. Nos. 810,348 and 811,797.

As polyamines, which are employed for the preparation of the reactivepolyamides, may be used aromatic polyamines or especially aliphaticpolyamines which can also contain heterocyclic structures such asimidazolines.

Reactive polyamides may also be condensation products of polymeric fattyacids with polyamines described in British Pat. Nos. 726,570 and 847,028which products may be reacted with epoxide resins derived by reactionfrom polyhydric phenols with polyfunctional halohydrins and/or glyceroldichlorhydrin and described in US. Pat. Nos. 2,585,115 and 2,589,245.

Also reactive polyamides form by condensation polymerization at hightemperatures between a reaction mixture containing polymeric fatty acids(made in accordance with British Pat. Nos. 878,985 and 841,554)monomeric fatty acids and lower polyalkylene polyamines may be usedaccording to the present invention.

Suitable reactive polyamide resins which may be used for the preparationof the polymeric phthalocyanine pigment derivatives according to theinvention are described, for instance, in British Pat. Nos. 726,570,810,348, 811,797, 847,028, 865,656 and 1,108,558, elg., the compoundssold commercially as Versamid 140, Versamid 125," Ancamide 400,

Advantageously, the polyamide is employed in considerable excess overthe stoichiometric proportion (calculated from the amine value) requiredto react with all of the chloromethyl groups in the chloromethylatedphthalocyanine. The excess reactive polyamide is desirable in order toremove at once hydrogen chloride formed during the reaction of polyamideand chloromethylated phthalocyanine compound.

The polyamides may be used in solution in an organic solvent, which mayfor instance be an aliphatic alcohol or an aliphatic ketone. Suitablealiphatic alcohols are, for example, methanol, ethanol, isopropanol,n-butyl alcohol or amyl alcohol and suitable aliphatic ketones includeacetone and methyl ethyl ketone. Tertiary bases such as pyridine andoptionally halogenated or nitrated aromatic hydrocarbons such asbenzene, trichlorobenzene or nitrobenzene may also be used as organicsolvent.

The present invention also provides a pigment composition comprising aphthalocyanine pigment having the tendency to flocculate and a minorproportion of a polymeric phthalocyanine pigment derivative made fromcondensation of a chloromethylated copper phthalocyanine and a polyamidehaving at least one reactive amino group, as hereinbefore defined.

In addition to the essential components defined hereinbefore, thepigment composition of the invention may contain a minor proportion ofchloromethylated phthalocyanine and reactive polyamide.

The pigment compositions of the present invention have goodflocculation-resistance and may be obtained by intimately incorporatingthe phthalocyanine pigment tending to flocculate with from 2 to 20percent by weight of the polymeric copper phthalocyanine derivative ashereinbefore defined. Incorporation of the above polymeric copperphthalocyanine derivative into the phthalocyanine pigment may be carriedout by various methods.

However, isolation of the polymeric copper phthalocyanine derivatives isnot a simple process. Therefore the flocculation-resistant pigmentcomposition according to the invention is preferably produced by millingtogether, in a single stage process, a liquid mixture comprising aphthalocyanine pigment having the tendency to flocculate, a minorproportion of a chloromethylated copper phthalocyanine compound and apolyamide having at least one reactive amino group, as hereinbeforedefined. This process has the considerable advantage that the polymericphthalocyanine derivative need not be isolated. Further in theexperiments carried out the resulting pigments had better performance incoating compositions than those produced by the addition of pre-preparedpolymeric phthalocyanine derivative.

Any phthalocyanine pigment having a tendency to flocculate may beemployed as a starting material in the process of the present invention.Thus the flocculating phthalocyanine may be unchlorinated orchlorinated, metal-free or metalliferous, the latter type containingsuch metals as nickel, cobalt or preferably copper. Of particularinterest, however, is copper phthalocyanine or its chlorinatedderivatives, containing from to percent chlorine, for instance themon-chloro copper phthalocyanine and metal-free phthalocyanine.

Suitable chloromethylated copper phthalocyanines and reactive polyamidesfor the single-stage manufacture of pigment composition of the inventionare those which are mentioned hereinbefore as suitable reactants in thecondensation to provide polymeric phthalocyanine pigment derivativesaccording to the invention.

The proportion of the chloromethylated phthalocyanine to that of theflocculating phthalocyanine employed in the single-stage process for theproduction of the pigment composition of the invention may be within therange of from 0.5 to 25 percent by weight, more preferably from 1 to 15percent by weight.

The flocculating phthalocyanine pigment may be employed in the formproduced in any of its various stages of manufacture, for instance incrude form, as filter cake or presscake, or especially as dry powder oras acid-pasted or salt-ground pigmentary material. However, for reasonsof economy, it is particularly preferred to use the flocculatingphthalocyanine in crude form.

As in the production of the polymeric phthalocyanine derivatives of theinvention, the polyamide is advantageously employed in the single-stagegrind in considerable excess, over the stoichiometric proportion(calculated from the amine value) required to react with all of thechloromethyl groups of the chloromethylated phthalocyanine.

Any suitable milling method may be employed such as sand grinding, ballmilling or Perl milling with the aid of corresponding grinding agentswhich include sand, gravel and glass beads.

Thus the production of a flocculation resistant pigment of the inventionis conveniently effected by charging the flocculating phthalocyanine,the chloromethylated phthalocyanine, the polyamide and the grinding aidinto a mill, and milling the mixture for a period, preferably within therange of from 5 to hours, depending on the mill system used. The liquidmilling is desirably effected in the presence of a diluting agent and atambient temperature, that is at a temperature within the range of from15 to 30 C., although higher temperatures can be used. Suitable dilutingagents are those described hereinbefore as solvents suitable for use inconjunction with reactive polyamide in the preparation of the polymericphthalocyanine derivatives of the invention. During the single-stagemilling processes of the invention, the reactive polyamide and thechloromethylated phthalocyanine are caused to react together and thereaction product formed in situ is incorporated into the flocculatingphthalocyanine all in the same operation. As a consequence, the millingprocess of the invention enjoys considerable economic advantages overknown processes in which pre-formed non-flocculating phthalocyanines areseparately incorporated into the flocculating phthalocyanine.

The pigment compositions produced according to the process of thepresent invention have high tinctorial power and exhibit excellentresistance to flocculation, for instance when incorporated intosurface-coating compositions such as medium or long oil alkyd paints,melamine formaldehyde modified alkyd paints or acrylic paints.

The following examples further illustrate the present invention. Partsby weight bear the same relation to parts by volume as do kilograms toliters.

EXAMPLES 1 to Eighteen parts by weight of dry crude monochloro copperphthalocyanine, 2 parts by weight of chloromethylated copperphthalocyanine (having a chlorine content in the range offrom 13 to 16percent by weight), a solution of 50 parts by weight of Versamid 140 (areactive polyamide of amine value 350-400 milligrams KOl-l/g.) in 150parts by weight of ethanol are ground with 650 parts by weight of gravelduring 65 hours. At the end of this time, the mixture is washed througha coarse (60 mesh) sieve with ethanol, filtered, washed thoroughly withethanol and acetone and dried.

The pigment composition so produced has high flocculation resistance insurface-coating compositions. A pigment composition produced when thechloromethylated copper phthalocyanine is replaced by 2 parts by weightof monochloro copper phthalocyanine, the remaining procedure being thatdescribed in Example l,'flocculatesb'adly in the same surface-coatingcompositions.

Pigment compositions having similar excellent flocculation resistance insurface-coating compositions are obtained when Versamid 140 is replacedby 50 parts by weight of one of the following resins:

Versamid 125 (amine value 290-320 milligrams KOH/g)(Example 2) Synolide960 (amine value 360-400 milligrams KOI-l/g)(Example 3) Ancamide 400(amine value 400-440 milligrams KO H/gXEXample 4) Beckalide K189 (aminevalue 400-420 milligrams KOH/gXExample 5) Genamid 250 (amine value245-450 milligrams KOH/g)( Example 6) Casamid 167 (amine value 430-470milligrams KOH/g)(Example 7) Merginamide L490 (amine value 480-500milligrams KOH/g)(Example 8) Genamide 2000 (amine value 575-625milligrams KOH/g) (Example 9) Wolfamid 4 (Amine value 360-400 milligramsKOH/ g) (Example 10) EXAMPLE 1 l Nineteen parts by weight of dry crudemonochloro copper phthalocyanine, 1 part by weight of chloromethylatedcopper phthalocyanine (having a chlorine content in the range from 13 to16 percent by weight), a solution of 50 parts by weight of Versamid 140(a reactive polyamide of amine value 350-400 milligrams KOl-l/g.) in 150parts by weight of ethanol are ground with650 parts by weight of gravelfor 65 hours. At the end of this time, the mixture is washed through acoarse (60 mesh) sieve with ethanol, filtered, washed thoroughly withethanol and acetone and dried.

The pigment composition so produced has high flocculation resistance insurface-coating compositions. A pigment composition produced when thechloromethylated copper phthalocyanine is replaced by 2 parts by weightof monochloro copper phthalocyanine, the remaining procedure being thatdescribed in Example I, flocculates badly in the same surface-coatingcompositions.

EXAMPLES 12 and 13 Eighteen parts by weight of dry crude monochlorocopper phthalocyanine,

two parts by weight of chloromethylated copper phthalocyanine (having achlorine content of 15 percent by weight), and

fifty parts by weight of Genamid 2000 in,

one hundred and fifty parts by weight of acetone are ground with 650parts by weight of gravel for 65 hours. At the end of this time thesample is recovered as in Example 1. The resulting pigment has excellentresistance to flocculation in surface-coating compositions. Pigmentproduced in a similar experiment, but in which the chloromethylatedcopper phthalocyanine is replaced by 2 parts by weight of' crudemonochloro copper phthalocyanine flocculates badly in the same coatingcompositions.

A flocculation-resistant pigment is also obtained when the acetone ofExample I2 is replaced by methanol (Example 13).

EXAMPLE l4 Eighteen parts by weight of crude monochloro copperphthalocyanine, 2 parts by weight of chloromethylated copperphthalocyanine (having a chlorine content of 15 percent by weight), asolution of 40 parts by weight of Versamid in parts by weight ofnitrobenzene are ground with 650 parts by weight of gravel for 65 hours.At the end of this time, the mixture is washed thoroughly through a 60mesh sieve with ethanol to remove the gravel. Afterwards the pigment isseparated by filtration, washed thoroughly with ethanol and dried.

The pigment composition so produced has good flocculation-resistance andhigh tinctorial power in coating compositions.

A pigment produced when the chloromethylated copper phthalocyanine isreplaced by 2.0 parts by weight of monochloro copper phthalocyanine, theremaining procedure being the described in the above example, has poorflocculation resistance and lower tinctorial power.

EXAMPLE l5 Eighteen parts by weight of dry crude monochloro copperphthalocyanine,

two parts by weight of chloromethylated copper phthalocyanine (having achlorine content of 13 percent by weight,

fifty parts by weight of Versamid 140 in,

one hundred and fifty parts by weight of ethanol, and

six hundred parts by weight of glass beads are charged to a Drais Perlmilled at low speed for 6 hours. The pigment is then separated from thebeads, filtered, washed thoroughly with ethanol and acetone and dried.

The pigment composition thus obtained has high tinctorial power andexcellent resistance to flocculation in surface-coating compositions.

EXAMPLES 16 to 19 Eighteen parts by weight of crude monochloro copperphthalocyanine, 2 parts by weight of chloromethylated copperphthalocyanine (having a chlorine content of 10 percent by weight), asolution of 100 parts by weight of Versamid 140, a reactive polyamideresin having an amine value of 350-400 milligrams KOH/g, in 100 parts byweight of ethanol are ground with 650 parts by weight of gravel for 65hours. At the end of this time, the mixture is washed thoroughly througha coarse (60 mesh) sieve with ethanol, filtered, washed thoroughly withethanol and acetone and dried.

The pigment composition so produced has high flocculation-resistance insurface-coating compositions. A pigment composition produced when thechloromethylated copper phthalocyanine is replaced by 2.0 parts byweight of monochloro copper phthalocyanine, the remaining procedurebeing that described in Example 16, flocculates badly in the samesurface-coating compositions.

Pigment compositions having similar excellent flocculation-resistance insurface-coating compositions are obtained when:

a. a solution of 50 parts by weight of reactive polyamide resin in 150parts by weight of ethanol is employed, the remaining conditions beingthe same as Example 16 (Example 17), or

b. a solution of 18 parts by weight of the reactive polyamide resin in182 parts by weight of ethanol is employed, the remaining conditionsbeing as defined in Example 16 (Example 18), or

c. the ethanol solvent in Example 16 is entirely replaced by the sameamount of isopropanol (Example l9).

EXAMPLE 20 Eighteen parts by weight of crude monochloro copperphthalocyanine,

two parts by weight of chloromethylated copper phthalocyanine (having achlorine content of percent by weight), and

twenty parts by weight of Genamid 250 in 180 parts by weight of ethanolare milled with,

six hundred and fifty parts by weight of gravel for 65 hours.

At the end of this time the pigment produced is recovered as inExample 1. It has excellent resistance to flocculation insurface-coating compositions.

EXAMPLE 21 A. Twenty parts by weight of chloromethylated copperphthalocyanine having a chlorine content of 12 percent by weight, 50parts by weight of Genamid 250 and 200 parts by weight of nitrobenzeneare ground with 650 parts by weight of gravel for 65 hours. At the endof this time the slurry is separated from the gravel by passing itthrough a 60 mesh sieve and washing with 500 parts by weight ofnitrobenzene.

B. A sample of a nitrobenzene slurry containing 25 parts by weight ofmonochloro copper phthalocyanine is stirred with 50 parts by weight of98 percent sulphuric acid for 2 hours at 60 C. The mixture is thendrowned out into 1,000 parts by weight of water, the nitrobenzene andpigment coalesce and this pigment/nitrobenzene mass is washed bysuccessive washings and decantations until the pH of the aqueous phaseis about 4. The pH is then raised to 7 by addition of aqueous sodiumhydroxide solution. The aqueous phase is finally decanted off.

C. Forty parts by weight of the nitrobenzene slurry obtained by grindingchloromethyl copper phthalocyanine with- Genamid 250 according to theabove paragraph A are added to the phthalocyanine/nitrobenzene massprepared according to paragraph B and the new mixture is refluxed withstirring for 8 hours. Afterwards the nitrobenzene is removed by steamdistillation and the pigment is filtered off, washed with water anddried.

The pigment thus produced has high tinctorial power and betterresistance to flocculation than a pigment prepared in a similar mannerbut from which the chloromethylated copper phthalocyanine has beenomitted.

EXAMPLE 22 Eighteen parts by weight of dry crude copper phthalocyanine,

two parts by weight of chloromethylated copper phthalocyanine (having achlorine content of 15% by weight), and

fifty parts by weight of Genamid 250 in 150 parts by weight of ethanol,are ground with six hundred and fifty parts by weight of gravel forhours.

At the end of this time the charge is washed through a 60-mesh sieve,filtered, thoroughly washed with ethanol and acetone and dried.

The pigment thus produced has better flocculationresistance than apigment produced in a similar experiment, but in which thechloromethylated copper phthalocyanine is replaced by 2 parts by weightof crude copper phthalocyanine.

EXAMPLE 23 Sixty-seven parts by weight of crude monochloro copperphthalocyanine in the form of a filtercake of which the liquid phase isnitrobenzene and containing 30 percent by weight of solid, 2 parts byweight of chloromethylated copper phthalocyanine (having a chlorinecontent of 15 percent by weight) and 40 parts by weight of Versamid inparts by weight of nitrobenzene are ground with 650 parts by weight ofsand for 100 hours. The sand is thenv removed by passing the dischargedmass through a 60-mesh sieve; the slurry is then filtered, washedthoroughly with ethanol and acetone and dried.

The pigment thus produced has high tinctorial power and excellentflocculation-resistance in surface coating compositions.

EXAMPLE 24 Eighteen parts by weight of dry crude metal-freephthalocyanine, 2 parts by weight of chloromethylated copperphthalocyanine (having a chlorine content of 12 percent by weight) and50 parts by weight of Genamid 250 in 150 parts by weight of ethanol areground with 650 parts by weight of sand for 65 hours. The sand is thenremoved by passing the mass through a 60-mesh sieve; the slurry is thenfiltered and washed thoroughly with ethanol and acetone and dried.

The resulting pigment has high tinctorial power and excellent resistanceto flocculation in surface coating compositions. A pigment prepared inan identical manner, but from which the chloromethylated copperphthalocyanine has been omitted flocculates badly.

What we claim is:

1. An anti-flocculation pigment additive consisting essentially of apolymeric phthalocyanine pigment derivative comprising a copperphthalocyanine nucleus linked through methylene groups to polyamideresins derived from polyamides having at least one reactive amino groupand an amine value of 250-650 milligrams of potassium hydroxide per gramof polyamide.

2. A process of producing a pigment composition comprising millingtogether in a single stage a liquid mixture comprising a phthalocyaninepigment having a tendency to flocculate with a minor proportion of theadditive as defined in claim 1.

3. The process as claimed in claim 1 wherein the diluting agent is analiphatic alcohol or ketone.

4. The additive as claimed in claim 1 wherein the methylene groups arepresent in an amount corresponding to l-30 percent by weight, based onthe weight of the phthalocyanine residue, of chlorine atoms linked tothe phthalocyanine nucleus through the methylene groups inchloromethylated copper phthalocyanine.

5. A pigment composition comprising a phthalocyanine pigment having atendency to flocculate and a minor proportion of the additive as claimedin claim 1.

6. The pigment composition as claimed in claim 5 copper phthalocyanine.

9. The process as claimed in claim 7 wherein the flocculatingphthalocyanine contains from 0 to 10 percent chlorine.

10. The process as claimed in claim 7 wherein the flocculatingphthalocyanine is a metal-free phthalocyanine pigment.

11. The process as claimed in claim 7 wherein the quantity of additivecorresponds to l-l5 percent by weight, based on the weight of theflocculating phthalocyanine pigment, of the chloromethylated copperphthalocyanine.

12. The process as claimed in claim 7 wherein the flocculatingphthalocyanine pigment is in crude form.

13. The process as claimed in claim 8 wherein the milling is conductedin the presence of a diluting agent at a temperature within the range offrom 15 to 30 C.

2. A process of producing a pigment composition comprising millingtogether in a single stage a liquid mixture comprising a phthalocyaninepigment having a tendency to flocculate with a minor proportion of theadditive as defined in claim
 1. 3. The process as claimed in claim 1wherein the diluting agent is an aliphatic alcohol or ketone.
 4. Theadditive as claimed in claim 1 wherein the methylene groups are presentin an amount corresponding to 10- 30 percent by weight, based on theweight of the phthalocyanine residue, of chlorine atoms linked to thephthalocyanine nucleus through the methylene groups in chloromethylatedcopper phthalocyanine.
 5. A pigment composition comprising aphthalocyanine pigment having a tendency to flocculate and a minorproportion of the additive as claimed in claim
 1. 6. The pigmentcomposition as claimed in claim 5 wherein a minor proportion ofunreacted chloromethylated phthalocyanine and reactive polyamide arealso present.
 7. A process of producing a pigment composition as definedin claim 5 comprising intimately milling together in a single stage aliquid mixture comprising phthalocyanine pigment having a tendency toflocculate with a minor proportion of the additive.
 8. The process asclaimed in claim 7 wherEin the flocculating phthalocyanine pigment ismonochloro copper phthalocyanine.
 9. The process as claimed in claim 7wherein the flocculating phthalocyanine contains from 0 to 10 percentchlorine.
 10. The process as claimed in claim 7 wherein the flocculatingphthalocyanine is a metal-free phthalocyanine pigment.
 11. The processas claimed in claim 7 wherein the quantity of additive corresponds to1-15 percent by weight, based on the weight of the flocculatingphthalocyanine pigment, of the chloromethylated copper phthalocyanine.12. The process as claimed in claim 7 wherein the flocculatingphthalocyanine pigment is in crude form.
 13. The process as claimed inclaim 8 wherein the milling is conducted in the presence of a dilutingagent at a temperature within the range of from 15* to 30* C.